Process for production of sugar from a cotton-containing textile

ABSTRACT

Cotton-containing textiles, such as “trash” feedstock in terms of end-of-life-cotton textiles, may be used to produce sugar without the same kinds of harsh pretreatments used for other biomasses, such as corn, grass sources, or wood. Disclosed is a process for production of sugar from a cotton-containing textile waste fabric comprising optionally mechanically pretreating the cotton-containing textile, pretreating the cotton-containing textile with an acid pretreatment to form a slurry, cooling the slurry, adding at least one base to the slurry, adding at least one additional acid to the slurry to form a buffer in situ, adding a hydrolysis enzyme, and optionally filtering the slurry.

CROSS-REFERENCE TO RELATED APPLICATIONS

This patent application is a divisional patent application of U.S.patent application Ser. No. 16/914,013, filed 26 Jun. 2020, which claimsthe benefit of U.S. Provisional Patent Application No. 62/869,485, filedon 1 Jul. 2019, the contents of each of which are incorporated byreference in their entirety.

FIELD OF THE INVENTION

This disclosure relates to a process for producing sugar fromcotton-containing textiles.

BACKGROUND OF THE INVENTION

Biomasses are bio-derived feedstocks utilized to typically make sugar orother value added products that in turn can be utilized in many chemicalor physical processes. Typically, biomasses must be pretreated first toopen the protective shell around the cellulose to allow an enzyme topenetrate the biomass and start to hydrolyze the cellulose or starchchains. There exists already an industry producing cellulosic and starchethanol that comes from biomass such as corn, grass sources, or wood.These biomass sources require land to grow, and the amount of sugarobtained is much lower than cotton textiles. Additionally, such sources(or feedstock) typically require harsh pretreatments to obtain thesugars from these sources. The use of such harsh pretreatments, in turn,requires rinsing and neutralization of the feedstock.

Because of the aggressive pretreatment required for cotton (plant,stalk, fibers etc.), cotton has not really been considered as a highvalue biomass feedstock. Additionally, cotton typically has a higherdegree of crystallinity that makes bioconversion even more challenging.However, cotton in the form of textiles is 90+% pure cellulose andsubsequently glucose that has already been processed and, if at the endof life of the consumer good, is essentially a free feedstock forbioprocessing. If end-of-life cotton garments are utilized instead ofbiomass grown for use as a feedstock, an environmental benefit isobtained, in addition to economic benefits, as long as the process isnot cost prohibitive.

Textile cotton or recycled textile cotton is defined as a collected rawmaterial (clothing at the end of its service life, scraps of fabricsfrom the garment industry, dust, etc.) that is a waste and the cottoncomponent by nature is composed of more than 90% cellulose (which can beconverted into sugar).

A use of textile cotton for producing ethanol is known from thepublication “Ethanol Production from Cotton-Based Waste Textiles”(JEIHANIPOUR AND TAHERZADEH M J, BIORESOURCES TECHNOLOGY, Vol. 100, No.2, published online on Aug. 23, 2008). However, the process that isdescribed, which provides in particular a chemical pretreatment stage,is not satisfactory in terms of yield and requires the use ofconcentrated products, which makes it not very economical and difficultto produce on the industrial scale. Additionally, the process ofJeihanipour found that alkali pretreatment applied to cotton waste wasmore effective than acid pretreatment. Finally, although the applicationof alkali pretreatment at lower temperature (−20-0° C.) enhanceshydrolysis efficiency, it may be impractical to facilitate in aproduction facility.

Similarly, it has been suggested to use concentratedN-methylmorpholine-N-oxide (NMMO) as a solvent for the pretreatment ofcotton textile waste fabric to disrupt the highly crystalline cellulosepolymeric network. Although the NMMO pretreatment has been found to beeffective, employing the pretreatment is costly due to the expense ofNMMO and extensive process steps required.

Traditionally, the cost of sugar from cellulose has been high, so it hasbeen slow to develop and commercialize. For production of sugar fromcotton textiles, it has been suggested to use exotic solvents, highlevels of acids, or high levels of caustic at low temperatures. However,these suggestions are not realistic solutions due to cost and additionalmaterials needed to neutralize high levels of acid or caustic,recovering and recycling solvents along with the costs of the solvents,and for caustic, maintaining a temperature near freezing. In addition toneutralizing the acid or caustic, the neutralized component needsfurther to be rinsed.

There exists therefore the need for a lower-cost, less-harsh method forproducing sugar suitable for production of ethanol or other value addedproducts from cotton textile waste.

SUMMARY OF THE INVENTION

Cotton textile waste from fabric has been found to be a promisingbiomass for the production of bioethanol as a renewable fuel source.According to this disclosure, cotton textiles, such as “trash” feedstockin terms of end-of-life-cotton textiles, may be used to produce sugarwithout the same kinds of harsh pretreatments used for other biomasses,such as corn, grass sources, or wood. It is known that cotton has highercrystallinity [than such other biomasses], which makes it challenging toobtain very high yields of sugar. Yet, despite having highercrystallinity, cotton in the form of cotton textiles can be used toobtain high yields of sugar.

The present inventors have discovered a process for production of sugarfrom a cotton textile waste fabric. The process for production of sugarfrom a cotton textile waste fabric begins with a mild acid pretreatmentstep to swell the cellulose structure and permit accessibility ofenzyme, followed by enzymatic degradation or hydrolysis(saccharification) of cellulose to produce sugars (e.g., glucose). Noharsh pretreatment occurs. Rather, the cotton-containing textile ispretreated with a mild acid, which turns into buffer for hydrolysisenzyme—wherein buffered pH helps maintain efficacy of the enzyme.Additionally, no rinsing or neutralization or recovery or reconstitutionof strong acids or bases or solvents is needed.

According to the disclosure, a process for production of sugar from acotton-containing textile comprises:

-   -   a. Optionally mechanically pretreating the cotton-containing        textile;    -   b. pretreating the cotton-containing textile with an acid        pretreatment at elevated temperature to form a cotton slurry;    -   c. cooling the cotton slurry from (b);    -   d. adding a base to the slurry from (c);    -   e. adding at least one additional acid to the cotton slurry to        form a buffer in situ;    -   f. adding at least one hydrolysis enzyme to the buffered cotton        slurry to initiate enzymatic hydrolysis of the slurry; and    -   g. optionally filtering the slurry from (f) to separate        hydrolysate from cotton residue.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 shows hydrolysis efficiencies determined for each of 32 cottontextile waste samples based on Cotton Residue analysis method. 100%cotton polyester samples are shown in black-outlined/no-fill columns,cotton/polyester blend samples are shown in horizontally stripedcolumns, cotton/viscose/nylon blend sample is shown in thecheckboard-column, and content-not-identified sample is shown in theupward diagonally striped column.

FIG. 2 shows efficiencies determined for each of 32 cotton textile wastesamples based on HPLC analysis method. 100% cotton polyester samples areshown in black-outlined/no-fill columns, cotton/polyester blend samplesare shown in horizontally striped columns, cotton/viscose/nylon blendsample is shown in the checkboard-column, content-not-identified sampleis shown in the upward diagonally striped column, and 100% polyestersample is shown in the black-filled column.

FIG. 3 shows hydrolysis efficiencies determined for each of 32 cottontextile waste samples based on RIDA® Cube analysis method. 100% cottonpolyester samples are shown in black-outlined/no-fill columns,cotton/polyester blend samples are shown in horizontally stripedcolumns, cotton/viscose/nylon blend sample is shown in thecheckboard-column, content-not-identified sample is shown in the upwarddiagonally striped column, and 100% polyester sample is shown in theblack-filled column.

FIG. 4 shows the stages of a 100% cotton waste sample, beginning withits initial garment form, that was hydrolyzed.

FIG. 5 shows hydrolysis efficiencies for a 100% cotton T-shirthydrolyzed (all methods).

DETAILED DESCRIPTION OF THE INVENTION

The processes of the present disclosure obtain high sugar yields fromcotton-containing textiles without the need for harsh pretreatment,neutralization, or rinsing steps.

According to the disclosure, a process for production of sugar from acotton-containing textile comprises, consists essentially of, orconsists of:

-   -   a. optionally mechanically pretreating the cotton-containing        textile, wherein mechanical pretreatment comprises, consists        essentially of, or consists of breaking down the        cotton-containing textile;    -   b. pretreating the cotton-containing textile with an acid        pretreatment at elevated temperature to form a cotton slurry;    -   c. cooling the cotton slurry from (b);    -   d. adding at least one base to the slurry from (c);    -   e. adding at least one additional acid to the cotton slurry to        form a buffer in situ;    -   f. adding at least one hydrolysis enzyme to the buffered cotton        slurry to initiate enzymatic hydrolysis of the slurry; and    -   g. optionally filtering the slurry from (f) to separate        hydrolysate from cotton residue.

In a first embodiment, a process for the production of sugar from acotton-containing textile, comprises, consists essentially of, orconsists of:

-   -   a. optionally mechanically pretreating the cotton-containing        textile, wherein mechanical pretreatment comprises, consists        essentially of, or consists of breaking down the        cotton-containing textile;    -   b. pretreating the cotton-containing textile with an acid        pretreatment at elevated temperature to form a cotton slurry;    -   c. cooling the cotton slurry from (b);    -   d. adding at least one base to the slurry from (c);    -   e. adding at least one additional acid to the slurry from (d) to        form a buffer in situ;    -   f. adding at least one hydrolysis enzyme to the buffered slurry        from (e) to initiate enzymatic hydrolysis of the slurry; and    -   g. filtering the slurry from (f) to separate hydrolysate from        residual cotton powder; and    -   h. fermenting the hydrolysate from (g) to form ethanol, or    -   g′. fermenting the slurry from (f) to form ethanol.

In an embodiment, a cotton-containing textile comprises cotton andcotton-blend garments, including, but not limited to, cotton-polyesterblend garments.

In an embodiment, step (a) comprises, consists essentially of, orconsists of mechanical pretreatment, which comprises, consistsessentially of, or consists of breaking down the cotton-containingtextile by conventional methods such as, but not limited to, grinding,shredding, cutting, chopping, or garneting. Mechanical pretreatmenteffectively physically breaks down the textile into smaller componentsand/or increases the surface area of the textile components and/orreduces crystallinity of the textile aiding in subsequent hydrolysis. Inan embodiment, mechanical pretreatment comprises grinding thecotton-containing textile into a powder, wherein average particle sizeof the powder is between about 0.10 mm and about 2.0 mm. In anotherembodiment, the average particle size of the powder is between about0.15 mm and about 1.60 mm. In another embodiment, the average particlesize of the powder is between about 0.20 mm and about 1.5 mm. In anotherembodiment, the average particle size of the powder is less than about2.0 mm. In another embodiment, the average particle size of the powderis less than about 1.70 mm.

The process of the disclosure may be also used for a cotton-containingtextile that is already mechanically pretreated. In an embodiment, theprocess of the disclosure may be used for a cotton-containing textilethat is already ground, shredded, cut, chopped, or garneted, forexample. In an embodiment, the process of the disclosure may be used fora cotton-containing textile that is already in the form of a powder. Inan embodiment, a process for the production of sugar from a mechanicallypretreated cotton-containing textile, comprises, consists essentiallyof, or consists of:

-   -   b. pretreating the mechanically pretreated cotton-containing        textile with an acid pretreatment at elevated temperature to        form a cotton slurry,    -   c. cooling the cotton slurry from (b),    -   d. adding at least one base to the slurry from (c),    -   e. adding at least one additional acid to the slurry from (d) to        form a buffer in situ,    -   f. adding at least one hydrolysis enzyme to the buffered slurry        from (e) to initiate enzymatic hydrolysis of the slurry, and    -   g. filtering the slurry from (d) to separate hydrolysate from        residual cotton powder    -   h. fermenting the residual cotton powder from (e) to form        ethanol, or    -   g′. fermenting the slurry from (e) to form ethanol.

In an embodiment, if the process of the disclosure is used for acotton-containing textile that is already in the form of a powder, anaverage particle size of the cotton-containing textile powder may bebetween about 0.10 mm and about 2.0 mm. In another embodiment, theaverage particle size of the powder is between about 0.15 mm and about1.60 mm. In another embodiment, the average particle size of the powderis between about 0.20 mm and about 1.5 mm. In another embodiment, theaverage particle size of the powder is less than about 2.0 mm. Inanother embodiment, the average particle size of the powder is less thanabout 1.70 mm.

In an embodiment, step (b) comprises, consists essentially of, orconsists of pretreating the cotton-containing textile (or mechanicallypretreated cotton-containing textile, if step (a) is performed) with anacid pretreatment at elevated temperature to form a cotton slurry. In anembodiment, the acid pretreatment comprises at least one acid. In anembodiment, the at least one acid comprises, consists essentially of, orconsists of a weak acid. Examples of weak acids include, but are notlimited to, phosphoric acid, citric acid, nitrous acid, lactic acid,benzoic acid, acetic acid, and carbonic acid. In an embodiment, incontrast to strong acids, the weak acids are acids known to notcompletely dissociate in water. In another embodiment, the at least oneacid used in the acid pretreatment comprises, consists essentially of,or consists of phosphoric acid. In an embodiment, the concentration ofthe at least one acid in step (b) is between about 0.01 M and about 0.5M, optionally between about 0.10 M and about 0.25 M, optionally betweenabout 0.15 M and about 0.20 M.

In an embodiment, in step (b), the at least one acid is added to thepowder at a liquor ratio in a range from about 2:1 to about 12:1,optionally in a range from about 4:1 to about 10:1, optionally at about6:1.

In an embodiment, step (b) does not comprise addition of a base—i.e., abase is not used in pre-treating the cotton-containing textile. In anembodiment, step (b) does not comprise a pretreatment that requiresneutralization from use of a strong acid or base, recovery of anysolvent or pretreatment aids, or rinsing steps necessitated from apretreatment that requires components to be removed before hydrolysisand/or fermentation.

In an embodiment, the elevated temperature in step (b) is in a rangefrom about 240° F. to about 410° F., optionally in a range from about250° F. to about 280° F., optionally in a range from about 260° F. toabout 270° F., optionally at about 265° F. Heating time in step (b) isin a range from about 0.5 to about 5 hours, optionally from about 1 toabout 3 hours, optionally about 2 hours. Agitators may optionally beadded to the slurry to enhance internal mixing of the slurry. Due to theacid pretreatment, the resulting slurry has a much lowered viscosity.

In an embodiment, step (c) comprises, consists essentially of, orconsists of cooling the slurry to a temperature in a range from about120° F. to about 160° F., optionally in a range from about 130° to about150° F., optionally at about 140° F.

In an embodiment, step (d) comprises, consists essentially of, orconsists of adding at least one base to the slurry from (c) andoptionally agitating the slurry. In an embodiment, the at least one basecomprises, consists essentially of, or consists of a strong base.Examples of strong bases include, but are not limited to, potassiumhydroxide, sodium hydroxide, barium hydroxide, cesium hydroxide,strontium hydroxide, lithium hydroxide, and rubidium hydroxide. Inanother embodiment, the at least one strong base used in step (d)comprises, consists essentially of, or consists of sodium hydroxide. Inan embodiment, the concentration of sodium hydroxide is in a range fromabout 0.01 M to about 0.5 M. In an embodiment, the concentration ofsodium hydroxide is sufficient to effectively neutralize the acidpreviously added. In an embodiment, the presence of sodium hydroxideneutralizes phosphoric acid to form sodium phosphate in situ. The slurryis then optionally agitated, optionally between 1 and 120 minutes, andat a temperature in a range from about 120° F. to about 160° F.,optionally in a range from about 130° to about 150° F., optionally atabout 140° F.

In an embodiment, step (e) comprises, consists essentially of, orconsists of adding at least one additional acid to the cotton slurryfrom step (d) to form a buffer in situ and optionally agitating theslurry. In an embodiment, the at least one additional acid used in step(e) comprises, consists essentially of, or consists of a weak acid.Examples of weak acids include, but are not limited to, phosphoric acid,citric acid, nitrous acid, lactic acid, benzoic acid, acetic acid, andcarbonic acid. In an embodiment, the weak acids do not completelydissociate in water. In another embodiment, the at least one additionalacid used in step (e) comprises, consists essentially of, or consists ofcitric acid. In an embodiment, citric acid from step (e) forms a bufferwith sodium phosphate from step (d). A citric acid and sodium phosphatebuffer is known as a McIlvaine buffer.

In an embodiment, the concentration of the at least one acid in step (f)is between about 0.001 M and about 1.0 M, optionally between about 0.010M and about 0.1 M, optionally between about 0.025 M and about 0.050 M.

In an embodiment, step (f) comprises, consists essentially of, orconsists of adding at least one hydrolysis enzyme to the buffered cottonslurry from (e) to initiate enzymatic hydrolysis of the slurry, andoptionally agitating the slurry. Enzymatic hydrolysis is carried oututilizing a cocktail combination of cellulase and β-glucosidase.Examples of hydrolysis enzymes include, but are not limited to, CTEC3(Cellic CTec3 by Novozymes), Novozyme 188, Cellulcast 1.5L, Spezyme-CP,cellulases (e.g., Cellulase AP3), and β-glucosidase. In an embodiment,after adding the hydrolysis cocktail, hydrolysis occurs for betweenabout 24 and about 120 hours, optionally for between about 48 and 80hours, optionally for about 72 hours. The slurry is optionally agitated.The temperature during hydrolysis is in a range from about 80° F. toabout 140° F., optionally in a range from about 110° to about 130° F.,optionally at about 120° F. In another embodiment, the temperatureduring hydrolysis may be about 86° F., about which temperaturesaccharification and fermentation may occur simultaneously.

In an embodiment, step (g) comprises, consists essentially of, orconsists of filtering the slurry from (f) to separate hydrolysate fromcotton residue. This filtering may be done by any conventional meansknown to those skilled in the art, such as, for example, those describedin U.S. Pat. No. 9,540,665, which is herein incorporated by reference.The cotton residue is then dried, for example in an oven, and weighedafter drying. In an embodiment, the cotton residue is dried in an ovenin a range from about 120° F. to about 180° F., optionally in a rangefrom about 140° to about 170° F., optionally at about 158° F. The dryingtime may optionally be at least about 2 hours, optionally in a rangefrom about 4 to about 48 hours, optionally in a range from about 10 toabout 24 hours, optionally at least about 16 hours.

In an embodiment, if filtering step (g) occurs, step (h) furthercomprises fermenting and saccharifying the hydrolysate from (g) to formethanol. Alternatively, if filtering step (g) does not occur, step (g′)comprises fermenting and saccharifying the slurry from (f) to formethanol.

In another embodiment, when step (h) or (g′) comprises fermenting andsaccharifying the hydrolysate from (g), or when step (g′) comprisesfermenting and saccharifying the slurry from (f), step (f) may furthercomprise combining the hydrolysis enzyme with yeast.

After drying, a conversion rate (or hydrolysis efficiency) may becalculated. For example, after drying, the cotton residue may be weighedat time=0 minutes and time≥15 minutes. The conversion rate is thencalculated based on the amount of cotton added and the weight of residueat time≥15 minutes. In an embodiment, HPLC and RIDA® Cube are analysismethods that may be used to measure glucose concentration of thesolution to calculate the hydrolysis efficiency.

In an embodiment, the hydrolysis efficiency is at least about 10%, atleast about 20%, at least about 30%, at least about 40%, at least about50%, at least about 51%, at least about 52%, at least about 53%, atleast about 54%, at least about 55%, at least about 56%, at least about57%, at least about 58%, at least about 59%, at least about 60%, atleast about 61%, at least about 62%, at least about 63%, at least about64%, at least about 65%, at least about 66%, at least about 67%, atleast about 68%, at least about 69%, at least about 70%, at least about71%, at least about 72%, at least about 73%, at leaset about 74%, atleast about 75%, at least about 76%, at least about 77%, at least about78%, at least about 79%, or at least about 80%. The hydrolysisefficiency may be determined in a manner known to one of skill in theart. Exemplary analysis methods include Cotton Residue, HPLC, and RIDA®Cube. In an embodiment, hydrolysis efficiency is determined using theRIDA® Cube method.

In an embodiment, the process for production of sugar from acotton-containing textile does not comprise a pretreatment that requiresneutralization from use of a strong acid or base, recovery of anysolvent or pretreatment aids, or rinsing steps necessitated from apretreatment that requires components to be removed before hydrolysisand/or fermentation.

In an embodiment, the temperature, concentration, and time valuesprovided above are representative and not restrictive. For example, thepH and buffering capacity may be adjusted by adjusting the concentrationof the acids and/or base(s). Similarly, the pretreatment time andtemperature may be shortened or extended. Finally, hydrolysis time maybe shortened or extended, thus increasing or lowering the amount ofenzyme needed. It is also possible to adjust the solids of the process(i.e., the liquor ratio).

EXAMPLES

A cotton containing textile is cut and ground into a powder using aThomas Wiley Mini-Mill grinder. The cotton powder is pretreated with18.22 g/L phosphoric acid at a 6:1 liquor ratio at 265° F. for 2 h in aRoaches Pyrotec dyeing machine. Ball bearings are added to enhanceinternal mixing of the cotton slurry. The acid pretreatment creates ahomogenous cotton slurry with much lowered viscosity. The pretreatedcotton slurries are cooled to 140° F., and to each slurry, 8.92 g/L ofNaOH is added. The caustic effectively converts the phosphoric acid toform sodium phosphate in situ. The slurry containing the pretreatedcotton, phosphoric acid and sodium hydroxide is circulated for 15 min at140° F. in the Roaches Pyrotec dyeing machine to form the sodiumphosphate.

Next, 8.50 g/L citric acid is added to each slurry, and the slurrycontaining the phosphoric acid, sodium hydroxide, and citric acid iscirculated again for 15 min at 140° F. in the Roaches Pyrotec dyeingmachine. The combination of the citric acid and sodium phosphate forms abuffer in the pretreated cotton slurry. Next, 10% owg of enzyme cocktail(10:1 liquor) is added to each slurry, and hydrolysis occurs for 72 h at120° F.

Table A of the disclosure sets forth 32 cotton textile waste samples andincludes percentage cotton, where applicable.

TABLE A Cotton textile waste hydrolyzed Sample Garment DescriptionTW1-31-S1 Chaps Black, White, and Blue Striped Polo Shirt (100% Cotton)TW1-31-S2 Brown King Size Sheets (100% Egyptian Cotton) TW1-31-S3Kirkland White and Blue Checkered Dress Shirt (100% Extra Long StapleCotton/ Non-Iron Resin Finish) TW1-31-S4 Fruit of the Loom Navy BlueT-Shirt (100% Cotton) TW1-31-S5 Merona Red Sweater with Jewel Embroidery(53% Cotton/40% Rayon/7% Nylon) TW1-31-S6 Ralph Lauren Classic Fit WhiteDress Shirt w/Red and Blue Checkers (100% Cotton) TW1-31-S7 Nautica Red,White, and Blue Checkered Dress Shirt (100% Cotton) TW1-31-S8 HanesBlack Beefy-Tee Long Sleeve Shirt (100% Preshrunk Cotton) TW1-32-S1Tommy Hilfiger Red, White, and Blue Long Sleeve Shirt (no label or labelfaded) TW1-32-S2 Chaps Ralph Lauren Red, White, and Blue Long SleeveShirt (100% Cotton) TW1-32-S3 Old Navy Red, White, and Blue Long SleeveShirt (100% Cotton) TW1-32-S4 Hanes White T-Shirt (100% Cotton)TW1-32-S5 Ralph Lauren Blue, Green, Red, and White Striped Dress Shirt(100% Cotton) TW1-32-S6 Ralph Lauren Blue and White Striped Dress Shirt(100% Cotton) TW1-32-S7 Ralph Lauren Pink, Green, Orange, Black, andWhite Dress Shirt (100% Cotton) TW1-33-S1 Black Croft and Barrow PoloShirt (100% Cotton/Easy Care) TW1-33-S2 Haggar Off-White Khaki Pant(100% Cotton/Resin Finish) TW1-33-S3 Green/Blue Pin Stripe Croft andBarrow Dress Shirt (100% Cotton/Resin Finish) TW1-33-S4 White GeorgePolo Shirt (60% Cotton/40% Polyester) TW1-33-S5 Blue Tommy HilfigerDress Shirt (100% Cotton) TW1-33-S6 Blue/White Chaps Dress Shirt (55%Cotton/45% Polyester/Regular Fit/Wrinkle-Free) TW1-33-S7; Green FadedGlory T-Shirt with Pocket TW1-34-S1; (100% Cotton) (no label or labelfaded) TW1-34-S2 TW1-33-S8 Levi's Light Blue Washed Jeans (100%Cotton/Relaxed Fit) TW1-35-S1 Urban Pipeline Light Blue Washed Jeans(with Holes) (100% Cotton/Relaxed Boot Cut) TW1-35-S2 Eddie Bauer TanKhaki Pant (100% Cotton) TW1-35-S3 Old Navy Grey Loose Cargo Pant (100%Cotton) TW1-35-S4 Dockers Off-White Khaki Pant (100% Cotton) TW1-35-S5Forsyth of Canada Pin Stripe White and Blue Dress Shirt (100%Cotton/Wrinkle- Free/2 ply 80's) TW1-35-S6 Joseph & Feiss Brown DressShirt (100% Cotton/Non-Iron Resin Finish) TW1-35-S7 Haggar Black KhakiPant (100% Cotton/Non-Iron Care) TW1-35-S8 Chaps Blue and Tan CheckeredDress Shirt (60% Cotton/40% Polyester/Easy Care) TW1-37-S13 ArnoldPalmer Pink and White Striped Polo Shirt (100% Polyester)

The hydrolysis efficiencies of these 32 cotton textile waste samplesusing the same conditions (i.e., 18.22 g/L H₃PO₄, 2 hours, 265° F.pretreatment; 10% enzyme cocktail enzymatic hydrolysis, 72 hours, 120°F.) were evaluated. FIGS. 1-3 show the hydrolysis efficienciesdetermined for each sample based on the Cotton Residue, HPLC, and RIDA®Cube analysis methods. The highest values observed were ca. 73-75%(RIDA® Cube method). TW1-33-S5, a 100% cotton dress shirt, was among thetop-2 samples with the highest hydrolysis efficiencies seen across allthree analysis methods (i.e., 70.6, 72.5 and 74.3% for Cotton Residue,HPLC, and RIDA® Cube methods, respectively), while TW1-37-13, a 100%polyester shirt, displayed the lowest values seen based on HPLC andRIDA® Cube methods (3.0 and 2.2%, respectively). The latter result wasanticipated due to the lack of hydrolysable bonds in polyester bycellulases and other enzymes present in the enzyme cocktail. The lowsugar levels detected were most likely due to the presence of reducingsugars from the enzymes. The next lowest values seen across all threeanalysis methods were for TW1-33-S1, a black 100% cotton shirt (i.e.,33.2, 35.2 and 34.3% for Cotton Residue, HPLC, and RIDA® Cube methods,respectively). The values seen among other all-black 100% cotton wastetextile samples were also low (ca. 47-51%). However, the values seenamong other dyed 100% cotton waste textile samples in many casesexceeded this range, suggesting the presence of the high concentrationof black dye in these samples may influence hydrolysis.

Of the thirty-two samples analyzed, twenty-six were 100% cotton. Theaverage hydrolysis efficiencies for the 100% cotton samples were 60.5,62.3, and 61.2% for Cotton Residue, HPLC, and RIDA® Cube methods,respectively. Four blends were analyzed (either cotton/polyester orcotton/viscose/nylon), and the treatment was effective for thehydrolysis of each (ca. 40-69%). It should be understood that the CottonResidue method gave considerably lower efficiencies for the blends ascompared to HPLC and RIDA® Cube. Additionally, efficiencies are givenbased on the total weight of the sample. In reality, nearly completeconversion of the theoretical amount of glucose in the blends wasobtained for the cotton/polyester blends. Similarly, TW1-31-S5, a red53/40/7 cotton/viscose/nylon sweater, displayed the highest efficienciesacross all three analysis methods (i.e., 68.5, 65.5 and 63.8% for CottonResidue, HPLC, and RIDA® Cube methods, respectively), and its efficiencywas comparable to multiple 100% cotton waste textile samples studied.This is attributed to the blend because the cellulose content (from bothcotton and viscose) was the highest, i.e., 93% theoretical glucose.However, the efficiency of the theoretical glucose is lower than thecotton/polyester blends. It is assumed this is due to higherconcentrations of enzyme with lowering the blend percentage of cotton,even though the amount of enzyme is based on sample size and kept thesame for all experiments.

FIG. 4 shows the stages of a 100% cotton waste sample (TW1-31-S3) thatwas hydrolyzed, beginning with its initial garment form: (1) initialgarment form, (2) milled powder form, (3) condition after acidpretreatment, (4) filtered form (top layer: cotton residue, filtrate:hydrolysate). For this particular sample, a maximum hydrolysisefficiency of 74.9% was achieved (RIDA® Cube method).

A 100% cotton T-shirt was exposed to a hydrolysis treatment after usinga high pressure and temperature reactor pretreatment and 5% or 10% owgenzyme cocktail, TW1-34-S1 and TW1-34-S2, respectively. The cotton shirtwas selected, because when hydrolyzed during preliminary studies,hydrolysis efficiencies between ca. 71-79% across all three analysismethods (Cotton Residue, HPLC, and RIDA® Cube) were achieved. FIG. 5shows the comparison of the results from hydrolyzing TW1-34-S1 andTW1-34-S2.

FIG. 5 also shows the results from the hydrolysis of TW1-33-S7, a samplefrom the same cotton T-shirt that was hydrolyzed without the use of ahigh pressure and temperature reactor and using 10% owg enzyme cocktail.The results show that the use of the reactor aided in an increase inhydrolysis efficiency. These results show it is possible to cut theenzyme dose by half from 10% to 5% on a garment and increase thepretreatment temperature and obtain almost comparable levels ofhydrolysis as the 10% enzyme dose at a lower pretreatment temperature.

Table B of the disclosure sets forth the hydrolysis efficiencies (in %)observed in the samples of Table A for each of the analysis methodsused: Cotton Residue, HPLC, and RIDA® Cube.

TABLE B Overview of hydrolysis experimental work and results pH BeforeHydrolysis Efficiency Addition of (%, Based on Method) Pretreatmentenzyme Hydrolysis pH After Cotton RIDA ® Sample Conditions cocktailConditions Hydrolysis Residue HPLC Cube TW1-31-S1 18.22 g/L 5.36 10%enzyme 5.13 59.8 65.5 67.0 TW1-31-S2 H₃PO₄ 5.62 cocktail 5.34 59.5 61.364.3 TW1-31-S3 (6:1 liquor 5.54 (10:1 liquor 5.42 62.2 63.6 74.9TW1-31-S4 ratio), 5.37 ratio), 5.14 67.7 67.0 71.1 TW1-31-S5 265° F., 2h 5.49 120° F., 72 h) 5.12 68.5 65.5 63.8 TW1-31-S6 5.52 5.26 66.8 68.473.4 TW1-31-S7 5.47 5.30 56.4 58.5 61.2 TW1-31-S8 5.49 5.13 48.1 49.750.7 TW1-32-S1 5.51 4.98 62.0 67.1 68.7 TW1-32-S2 5.53 5.04 54.5 57.648.4 TW1-32-S3 5.28 4.85 67.0 65.9 64.0 TW1-32-S4 5.51 5.23 57.7 53.353.7 TW1-32-S5 5.42 5.10 67.5 71.3 56.8 TW1-32-S6 5.03 5.11 50.7 57.459.8 TW1-32-S7 5.45 5.10 65.6 68.2 71.3 TW1-33-S1 5.30 5.04 33.2 35.234.3 TW1-33-S2 5.53 5.40 60.0 60.8 61.4 TW1-33-S3 5.45 5.49 60.7 58.952.5 TW1-33-S4 5.32 5.28 43.2 61.4 62.7 TW1-33-S5 5.33 5.15 70.6 72.574.3 TW1-33-S6 5.30 5.23 39.9 49.8 50.8 TW1-33-S7 5.32 5.16 70.4 71.867.0 TW1-33-S8 5.15 5.08 62.5 67.9 62.0 TW1-35-S1 5.38 4.90 65.7 70.653.3 TW1-35-S2 5.40 5.18 62.6 66.7 65.2 TW1-35-S3 5.36 5.21 68.1 70.664.0 TW1-35-S4 5.47 5.40 64.2 64.4 66.6 TW1-35-S5 5.44 5.34 64.3 64.468.7 TW1-35-S6 5.54 5.51 58.7 56.8 58.1 TW1-35-S7 5.31 5.21 47.4 50.547.4 TW1-35-S8 5.39 5.25 42.8 51.8 52.6 TW1-37-S13 5.46 5.40 — 3.0 2.2TW1-34-S1 18.22 g/L 5.40 5% enzyme 5.27 63.51 66.00 68.60 H₃PO₄ cocktail(6:1 liquor ratio), (10:1 liquor ratio), 265° F., 3 h/ 120° F., 72 h)TW1-34-S2 338° F., 1.5 h 5.36 10% enzyme 5.26 75.00 76.54 76.40 cocktail(10:1 liquor ratio), 120° F., 72 h)

It is apparent that embodiments other than those expressly describedherein come within the spirit and scope of the present claims.Accordingly, the present invention is not defined by the abovedescription, but is to be accorded the full scope of the claims so as toembrace any and all equivalent compositions and methods.

1. A process for production of sugar from a cotton-containing textile,comprising: a. optionally mechanically pretreating the cotton-containingtextile, wherein mechanical pretreatment comprises breaking down thecotton-containing textile; b. pretreating the cotton-containing textilewith an acid pretreatment at elevated temperature to form a cottonslurry; c. cooling the cotton slurry from (b); d. adding at least onebase to the slurry from (c); e. adding at least one additional acid tothe slurry from (d) to form a buffer in situ; f. adding at least onehydrolysis enzyme to the buffered slurry from (e) to initiate enzymatichydrolysis of the slurry; and g. optionally filtering the slurry from(f) to separate hydrolysate from residual cotton.
 2. (canceled) 3.(canceled)
 4. (canceled)
 5. (canceled)
 6. (canceled)
 7. (canceled) 8.(canceled)
 9. A process for the production of sugar from acotton-containing textile comprising: a. optionally mechanicallypretreating the cotton-containing textile, wherein mechanicalpretreatment comprises breaking down the cotton-containing textile; b.pretreating the cotton-containing textile with an acid pretreatment atelevated temperature to form a cotton slurry; c. cooling the cottonslurry from (b); d. adding at least one base to the slurry from (c); e.adding at least one additional acid to the slurry from (d) to form abuffer in situ; f. adding at least one hydrolysis enzyme to the bufferedslurry from (e) to initiate enzymatic hydrolysis of the slurry; and g.filtering the slurry from (f) to separate hydrolysate from cottonresidue; and h. fermenting the hydrolysate from (g) to form ethanol; org′. fermenting the slurry from (f) to form ethanol.
 10. The process ofclaim 9, wherein (h) comprises fermenting and saccharifying thehydrolysate from (g) to form ethanol, or wherein (g′) comprisesfermenting and saccharifying the slurry from (f) to form ethanol. 11.The process of claim 10, wherein (f) further comprises combining thehydrolysis enzyme with yeast.
 12. The process of claim 9, wherein (a) isperformed.
 13. The process of claim 12, wherein in (a), said breakingdown comprises grinding, shredding, cutting, chopping, or garneting. 14.The process of claim 12, wherein in (a), said breaking down comprisesgrinding.
 15. The process of claim 9, wherein hydrolysis efficiency isat least 50%.
 16. The process of claim 9, wherein hydrolysis efficiencyis at least 60%.
 17. The process of claim 9, wherein hydrolysisefficiency is at least 65%.
 18. The process of claim 9, whereinhydrolysis efficiency is at least 70%.
 19. A process for production ofsugar from a mechanically pretreated cotton-containing textilecomprising: b. pretreating the mechanically pretreated cotton-containingtextile with an acid pretreatment at elevated temperature to form acotton slurry, c. cooling the cotton slurry from (b), d. adding at leastone base to the slurry from (c), e. adding at least one additional acidto the slurry from (d) to form a buffer in situ, f. adding at least onehydrolysis enzyme to the buffered slurry from (e) to initiate enzymatichydrolysis of the slurry, and g. filtering the slurry from (d) toseparate hydrolysate from cotton residue, and h. fermenting the residualcotton hydrolysate from (e) to form ethanol, or g′. fermenting theslurry from (e) to form ethanol.
 20. The process of claim 19, whereinthe mechanically pretreated cotton-containing textile is in the form ofa powder.
 21. The process of claim 20, wherein an average particle sizeof the powder is between about 0.10 mm and about 2.0 mm.